CN103872342B - Solid oxide fuel cell - Google Patents
Solid oxide fuel cell Download PDFInfo
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- CN103872342B CN103872342B CN201310669561.6A CN201310669561A CN103872342B CN 103872342 B CN103872342 B CN 103872342B CN 201310669561 A CN201310669561 A CN 201310669561A CN 103872342 B CN103872342 B CN 103872342B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
- H01M4/8885—Sintering or firing
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
- H01M4/8621—Porous electrodes containing only metallic or ceramic material, e.g. made by sintering or sputtering
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
- H01M4/8885—Sintering or firing
- H01M4/8889—Cosintering or cofiring of a catalytic active layer with another type of layer
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
- H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
- H01M4/9033—Complex oxides, optionally doped, of the type M1MeO3, M1 being an alkaline earth metal or a rare earth, Me being a metal, e.g. perovskites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/22—Fuel cells in which the fuel is based on materials comprising carbon or oxygen or hydrogen and other elements; Fuel cells in which the fuel is based on materials comprising only elements other than carbon, oxygen or hydrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide electrolytes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
- H01M8/1253—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing zirconium oxide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
Disclosed is a durable solid oxide fuel cell that is less likely to have a problem of a conventional solid oxide fuel cell that an air electrode containing a peroviskite oxide, when exposed to a reducing atmosphere, is separated at the stop of operation, especially shutdown. The solid oxide fuel cell includes an air electrode that is obtained by firing a compact containing a perovskite oxide and sulfur element. The content of the sulfur element in the air electrode as fresh after firing or before the start of power generation is in the range of 50 ppm to 3,000 ppm. The separation of the air electrode is effectively suppressed at the shutdown operation.
Description
Technical field
The present invention relates to a kind of SOFC monocell and possess the fuel-cell single-cell and constitute
Fuel cell system, can prevent the air pole run when stopping when especially shutting down from peeling off.
Background technology
In existing fuel cell, there is a kind of solid oxide fuel that soild oxide is used for solid electrolyte
Battery（Solid Oxide Fuel Cell:SOFC）.
Further, it is known to which one kind uses lanthanum-strontium Conjugate ferrite as air pole（LSCF）SOFC
（Such as Japanese Laid-Open 2001-196083 publication（Patent documentation 1））.And, exist LSCF contained by the air pole because
The SOx contained in the air contacted with air pole especially SO2Sulfur and the report be poisoned（Wang etal.,
J.Electrochem.Soc.,158,B1391(2011)）（Non-patent literature 1）.The document is reported in and is used as air pole
In the SOFC monocell of LSCF, sulfur reacts with the Sr of LSCF and is formed on LSCF surfaces
SrSO4, thus power generation performance decline.But, it is front in the use of SOFC according to known to the present inventor, and
The report of the presence of sulfur certainly in air pole.
Patent documentation 1：Japanese Laid-Open 2001-196083 publication
Non-patent literature 1：Wang et al.,J.Electrochem.Soc.,158,B1391(2011)
According to the experiment that the present inventor is carried out, especially observe containing Ca-Ti ore type oxidation in shutdown when operation stops
Thing and the stripping of air pole that constitutes.The stripping declines the durability of SOFC monocell, or even has
When the monocell can lose power generation performance.This has obtained following opinion to the present inventor, can be specific by containing air pole
The sulfur of amount and suppress the stripping.
The content of the invention
Thus, it is an object of the invention to provide a kind of have the solid oxidation of durability by suppressing air pole to peel off
Thing type fuel-cell single-cell.
Further, it is an object of the invention to provide a kind of SOFC monocell based on the present invention
Manufacture method and the fuel cell system for possessing the fuel-cell single-cell and constituting.
And, the present invention SOFC monocell be at least have solid electrolyte, fuel electrodes and
Air pole and the SOFC monocell that constitutes, it is characterised in that the air pole is to containing perovskite
The formed body of type oxide and element sulphur is burnt till and is constituted, after just burning till or generate electricity start before the air pole
In sulfur content be more than 50ppm and below 3,000ppm.
And, the fuel cell system of the present invention is characterised by possessing the solid oxide fuel of the invention described above
Cell single cells and constitute.
And, the manufacture method of the SOFC monocell of the present invention is characterised by, prepares calcium titanium
The material powder of sulphur compound is added with ore deposit type oxide, the material powder is disperseed in a solvent so as to prepare slurry,
The slurry is coated on solid electrolyte or its precursor, and after being dried, is burnt till to prepare air pole.
And, the manufacture method of another SOFC monocell of the invention is characterised by, right
The mixture that sulphur compound is added with the preparing raw material of perofskite type oxide is burnt till, so as to obtain containing element sulphur
Perofskite type oxide, crush the perofskite type oxide and obtain material powder, the material powder is dispersed in molten
So as to prepare slurry in agent, the slurry is coated on solid electrolyte or its precursor, and after being dried, is burnt till and
Prepare air pole.
Description of the drawings
Fig. 1 is the ideograph of a form of the section of the SOFC monocell for representing the present invention.
Fig. 2 is the partial sectional view of the fuel-cell single-cell unit for representing the present invention.
Fig. 3 is the solid oxide fuel cell system for representing the SOFC for possessing the present invention
The pie graph of one form.
Fig. 4 is the side view cutaway drawing of the fuel cell module for representing solid oxide fuel cell system.
Fig. 5 is the axonometric chart of the fuel cell pile for representing solid oxide fuel cell system.
Fig. 6 is the sectional view of the III-III lines along Fig. 4.
Specific embodiment
Definition
The fuel-cell single-cell of the present invention is referred in addition to air pole meets essential condition described later, is at least possess combustion
Material pole, solid electrolyte and air pole and constitute with the industry in be usually classified or be interpreted as solid oxide fuel electricity
Pond monocell identical fuel-cell single-cell.And, the fuel-cell single-cell of the present invention can be used for accordingly quilt in the industry
It is interpreted as fuel cell system and the system that can be understood from now on.In addition, the fuel-cell single-cell of the present invention is not limited
Its shape, for example, can also be cylindrical shape, tabular, internally be formed with hollow platy of multiple gas flow paths etc..In addition, inner side
Electrode can also be formed on the surface of supporter.
In addition, in the present invention, " before generating starts " is referred to after the burning till of fuel-cell single-cell, and carries out actual fortune
Before row.Even in addition, after testing after trial operation, before shipment or after the operation suitable with them, as long as they are in reality
Before border operation starts, then similarly it is considered as before generating starts.
In addition, in the present invention, " operation stops " referring to generally stop and shut down to stop.Generally stop based on generally
Draw to carry out, to avoid producing harmful effect to fuel-cell single-cell as far as possible.Shutdown stops then needing to be stood in system exception
It is i.e. out of service, and stop the supply of fuel and air immediately.
Air pole
In the present invention, air pole is the formed body containing perofskite type oxide and element sulphur to be burnt till and is constituted
, after just burning till or generate electricity start before aforementioned air extremely in sulfur content be more than 50ppm 3,000ppm with
Under.The lower limit of sulfur content is preferably more than 100ppm, more preferably more than 200ppm, its upper limit be preferably 3000ppm with
Under.By making sulfur content in above range, high power generation performance can be kept, and effectively prevent operation from especially closing when stopping
Air pole during machine is peeled off.Although effectively preventing operation from especially shutting down when stopping in above range by making sulfur content
When air pole it is not clear and definite the reasons why peel off, but can be following to consider.The SOFC list of the present invention
Air pole in battery be the formed body containing element sulphur is burnt till obtained from.It is therefore believed that the air pole of the present invention
In the existing way of element sulphur that contains it is at least different from the presence of the sulfur obtained from air because of generator operation.Further,
According to the opinion obtained by the present inventor, it is believed that the reason that air pole is peeled off is that air pole is sudden and violent when operation stops
In being exposed to reducing atmosphere.That is, due to supplying air, therefore fuel electrodes to fuel electrodes supply fuel gas and to air pole during operation
In being exposed to reducing atmosphere, air pole is exposed in oxidizing atmosphere.On the other hand, when operation stops, interrupts fuel gas
After body, the supply of air, the fuel gas in fuel distribution tube, reformer, fuel diverter is remained in sometimes from fuel gas stream
The outlet on road is that monocell peristome sprays to air pole, so that air pole is exposed in reducing atmosphere.Due to air pole quilt
In being exposed to reducing atmosphere, thus it is possible to cause air pole to peel off.
In the present invention, air pole is the formed body containing perofskite type oxide and element sulphur to be burnt till and is constituted
's.And, if element sulphur is present in formed body before burning till, both can come from separately coordinating with perofskite type oxide
Sulphur compound, it is also possible to the sulphur compound contained in the preparing raw material of perofskite type oxide.
In the present invention, as the perofskite type oxide for constituting air pole, La can be enumerated1-xSrxCoO3（But x=0.1
~0.3）And LaCo1-xNixO3（But x=0.1~0.6）Deng lanthanum cobalt system oxide,（La、Sr）FeO3System and（La、Sr）CoO3
The solid solution of system is lanthanum Conjugate ferrite system oxide（La1-mSrmCo1-nFenO3（But 0.05<m<0.50、0≤n≤1））, contain
The SmCo system oxide of samarium and cobalt（Sm0.5Sr0.5CoO3）Deng.Preferably lanthanum-strontium Conjugate ferrite（LSCF）.
In the present invention, sulphur compound can also be any one of organosulfur compound, inorganic sulfide compound.As having
The concrete example of organic sulfur compound, can enumerate naphthalene sulfonic acid-formaldehyde condensation product, DBSA, dodecylbenzene sodium sulfonate, alkane
Base sodium naphthalene sulfonate, dialkyl sodium sulfosuccinate, alkyl diphenyl ether disulphonic acid sodium, sodium alkanesulfonate, polyoxyalkylene alkenyl
It is ether ammonium sulfate, beta-naphthalenesulfonic-acid formaldehyde condensation compound, sodium lauryl sulphate, alkyl sodium sulfate, dodecyltriethanolamine sulfate, poly-
The work of oxygen vinyl alkyl ether sodium sulfate, sodium laureth sulfate, polyoxyethylene alkyl ether sulphuric acid triethanolamine etc.
Known compound, dimethyl sulfide, allyl sulphide etc. for surfactant.In addition, can also utilize in the present invention
The low molecular peptide of aminoacid, the glutathion of cysteine, methionine, homocysteine, taurine etc. etc..
As the concrete example of inorganic sulfide compound, cadmium sulfide, zinc sulfide, iron sulfide, ferrous disulfide, curing can be enumerated
Molybdenum, pyrite, molybdenite, Chalkopyrite, galena, cinnabar, sodium disulfide, Carbon bisulfide, five calcium sulfides, calcium sulfide, titanium dioxide
Sulfur, sulfur trioxide, sulfur hexafluoride, sulfur dichloride, hydrogen sulfide, barium sulfate, sodium thiosulfate, can also enumerate sulfur oxyacid i.e. sulfurous
Acid, sulphuric acid, permonosulphuric acid, thiosulfuric acid, hydrosulfurous acid, pyrosulfurous acid, dithionic acid, pyrosulfuric acid, even peroxy-disulfuric acid, many sulfur
Acid.
In a form of the present invention, preferably by the sulphur compound with the function as surfactant.Pass through
Sulphur compound has the function of surfactant, so that element sulphur is evenly dispersed in the material of air pole.It is thus regarded that
Good air pole can be prepared, can effectively prevent from peeling off.
In the present invention, air pole both can be monolayer, or multilamellar.As example during multi-layer air pole, example
Can such as enumerate and La is set on the solid electrolyte0.6Sr0.4Co0.2Fe0.8O3As air pole catalyst layer, in fuel cell list electricity
La is set on the most top layer in pond0.6Sr0.4Co0.8Fe0.2O3As the composition of air pole.
Fuel electrodes
In the present invention, as long as fuel-cell single-cell can be constituted together with above-mentioned air pole then not special for fuel electrodes
It is defined, for example, can enumerates NiO/ containing Zirconium oxide, NiO/ containing cerium oxide etc..Here, NiO/ refers to NiO containing Zirconium oxide
With uniformly mixed with requirement ratio containing Zirconium oxide.In addition, NiO/ refers to NiO and containing cerium oxide with regulation ratio containing cerium oxide
Rate uniformly mixes.For example can enumerate doped with CaO, Y containing Zirconium oxide containing Zirconium oxide as NiO/2O3、Sc2O3In one
Kind more than containing Zirconium oxide etc..In addition, containing cerium oxide formula Ce can be enumerated containing cerium oxide as NiO/1-yLnyO2
（But Ln is any one in La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc, Y or two or more
Combination, 0.05≤y≤0.50）Deng.Further, since NiO is reduced under fuel atmosphere and becomes Ni, therefore said mixture point
Do not become Ni/ and contain cerium oxide containing Zirconium oxide or Ni/.
In the present invention, fuel electrodes both can be monolayer, or multilamellar.As example during multilamellar fuel electrodes, example
Can such as be set forth in and there is Ni/YSZ with supporter opposite side（Yttria-stabilized zirconia）Layer fuel electrodes or with solid
Electrolyte opposite side has Ni/GDC（Gd2O3-CeO2）（Play a role as fuel electrode catalyst layer）Layer fuel electrodes, enter
And there are the fuel electrodes of the layer of above-mentioned both sides.
Solid electrolyte
In the present invention, as long as solid electrolyte can constitute fuel-cell single-cell then not together with above-mentioned air pole
Especially be defined, for example can enumerate gallic acid lanthanide oxide, as solid solution species solid solution have in Y, Ca, Sc any one with
On stabilizing zirconia etc..Solid electrolyte is ideally the gallic acid lanthanide oxide doped with Sr and Mg, it may be more desirable to by
Formula La1-aSraGa1-b-cMgbCocO3（But 0.05≤a≤0.3,0<b<0.3、0≤c≤0.15）The gallic acid group of the lanthanides oxygen of expression
Compound（LSGM）.A preferred configuration of the invention, it is also possible between solid electrolyte and fuel electrodes, as reaction suppression
Preparative layer arranges the cerium system oxide for making La be solid-solution in ceria（Ce1-xLaxO2（But 0.3<x<0.5））.Reaction inhibiting layer is excellent
Choosing is Ce0.6La0.4O2。
In the present invention, solid electrolyte can be monolayer, or multilamellar.When as solid electrolyte being multilamellar
Example, for example, can be set forth in fuel electrodes and arrange Ce and the solid electrolyte that is made up of LSGM between0.6La0.4O2Deng response inhabitation
The composition of layer.
Fuel-cell single-cell
Fig. 1 is the ideograph of a form of the section of the SOFC monocell for representing the present invention,
The type for making medial electrode be fuel electrodes is shown.SOFC monocell 210 in the present invention is for example by more
Hole matter supporter 201,（First/second）Fuel electrodes 202,（First/second）Solid electrolyte 203,（First/second）Air pole
204 and current collection layer 205 constitute.Here,（First/second）Refer to " there is the in the case of layer more than monolayer or two-layer, two-layer
One layer and the second layer ".In the SOFC monocell of the present invention, the preferred thickness of each layer is, Porous
Supporter is 0.5~2mm, and extremely 10~200 μm of fuel, fuel electrode catalyst layer is 0~30 μm, and reaction inhibiting layer is 0~20 μ
M, solid electrolyte is 5~60 μm, and air pole catalyst layer is 0~50 μm, extremely 10~200 μm of air.
Fig. 2 is the partial sectional view of the fuel-cell single-cell unit for representing the present invention.As illustrated, fuel cell list is electric
Pool unit 16 possesses fuel-cell single-cell 84 and is connected to the interior of the above-below direction end of the fuel-cell single-cell 84
Lateral electrode terminal 86 and constitute.Fuel-cell single-cell 84 is the tubular body structure for extending in the vertical direction, is internally formed
Possess medial electrode layer 90, lateral electrode layer 92 on the cylindrical porous matter supporter 91 of fuel gas channel 88, positioned at inner side
Solid electrolyte 94 between electrode layer 90 and lateral electrode layer 92 and constitute.
Because the upper end side installed in fuel-cell single-cell 84 is identical structure with the medial electrode terminal 86 of lower end side,
So here specifically describes the medial electrode terminal 86 for being installed on upper end side.The top 90a of medial electrode layer 90 possesses relatively
The outer peripheral face 90b exposed in solid electrolyte layer 94 and lateral electrode layer 92 and upper surface 90c.Medial electrode terminal 86 is across leading
Electrically encapsulant 96 is connected with the outer peripheral face 90b of medial electrode layer 90, and then, by the upper surface with medial electrode layer 90
90c directly contacts and electrically connect with medial electrode layer 90.It is formed with and medial electrode layer in the central part of medial electrode terminal 86
The fuel gas channel 98 of 90 connection of fuel gas channel 88.
The manufacture method of monocell
The SOFC monocell of the present invention, can be according to public affairs in addition to making air pole contain element sulphur
The method known suitably is manufactured.If illustrating that preferred manufacturer's rule is as described below.
First, air pole can be as follows obtained in the present invention, solvent is added in material powder（Water, ethanol etc.）, dispersion
The shaping additive of agent, binding agent etc. is coated onto on solid electrolyte or its precursor making slurry, is burnt till after being dried
（Preferably 1000 DEG C less than 1200 DEG C）.Here, " being coated on solid electrolyte or its precursor " refer to be not limited to by
Slurry is applied directly on solid electrolyte or its precursor, for example, also include the intermediate layer as catalyst layer and be coated in
Form on solid electrolyte or its precursor.In addition, as described later, precursor is referred to solid electrolyte and air pole while carrying out
The form burnt altogether, it is meant that become material or formed body before the burning till of solid electrolyte by burning till.
First form of manufacturing method according to the invention, mixing perofskite type oxide and sulphur compound carry out preparing raw material
Powder.Slurry is prepared using the material powder.In addition, other forms of the invention, in the preparation of perofskite type oxide
Mix sulphur compound in raw material and obtain mixture.The mixture is burnt till（Preferably 1100 DEG C less than 1250
℃）, so as to obtain the perofskite type oxide containing element sulphur.It is crushed and preparing raw material powder.Using the raw material
Powder prepares slurry.Here, the preparing raw material of perofskite type oxide is referred to for preparing desired Ca-Ti ore type oxidation
The mixed material of raw material of thing.Either any form, as sulphur compound above-mentioned organic sulfur chemical combination can be used
Thing or inorganic sulfide compound.
Coating can well be carried out by slurry coating method, the tape casting, doctor blade method, transfer printing of coating materials feed liquid etc..
Alternatively, it is also possible to utilize printing process, it is possible to use screen painting method, ink-jet method etc..
Solid electrolyte, fuel electrodes can be as follows obtained, in each material powder solvent is added（Water, ethanol etc.）, dispersant,
The shaping additive of binding agent etc. coats the slurry making slurry, is burnt till after being dried（1100 DEG C less than 1400
℃）.Coating can well be carried out by slurry coating method, the tape casting, doctor blade method, transfer printing of coating materials feed liquid etc..In addition,
Printing process can also be utilized, it is possible to use screen painting method, ink-jet method etc..
Although burn till can also carry out when each electrode and solid electrolyte is formed every time, can also carry out " altogether
Burn ", i.e., multiple layers are disposably burnt till.Additionally, it is preferred that burn till carried out under oxidizing atmosphere, with avoid solid electrolyte because
Diffusion of dopant etc. and degeneration.More preferably using the mixed gas of air and oxygen, more than mass % of oxygen concentration 20 and 30
Burnt till under atmosphere below quality %.
Preferred configuration of the invention is right when air pole is used for into lateral electrode when fuel electrodes are used for into medial electrode
Fuel electrodes and solid electrolyte carry out after common burning, shaping air pole, to be burnt till less than the temperature burnt altogether.
SOFC monocell and the fuel cell system using the fuel-cell single-cell
According to the present invention, there is provided a kind of solid oxygen for possessing the SOFC monocell based on the present invention
Compound type fuel cell system.Fig. 3 is the structure of the solid oxide fuel cell system for representing one embodiment of the present invention
Cheng Tu.As shown in Figure 3, solid oxide fuel cell system 1 possess fuel cell module 2 and auxiliary equipment unit 4 and
Constitute.
Fuel cell module 2 possesses housing 6, and sealing space 8 is formed with across adiabator 7 inside the housing 6.Separately
Outward, it is also possible to be not provided with adiabator.The section below of the sealing space 8 be power compartment 10 be configured with using fuel gas and
Oxidant（Air）Carry out the aggregate 12 of electric power generation reaction.The aggregate 12 possesses
10 fuel cell piles 14（With reference to Fig. 5）, the fuel cell pile 14 is by 16 fuel-cell single-cell units 16（Reference picture
2）Constitute.Thus, aggregate 12 has 160 fuel-cell single-cell units 16, these fuel cells
Single cell units 16 are all connected in series.
Combuster 18, electric power generation reaction are formed in the top of the above-mentioned power compartment 10 of the sealing space 8 of fuel cell module 2
In untapped remaining fuel gas and remaining oxidant（Air）The burning in the combustor 18, generates discharge gas.
And, the reformer 20 reformed to fuel gas is configured with the top of the combustor 18, using aforementioned residual gas
Reformer 20 is heated to be calory burning the temperature that can carry out reforming reaction.And, it is free in the top configuration of the reformer 20
Gas heat exchanger 22, for receiving the heat of reformer 20 to add hot-air, suppresses the temperature drop of reformer 20.
Next, auxiliary equipment unit 4 possesses：Pure water tank 26, stores the water from the waterings such as water pipe 24 and passed through
Filter becomes pure water；And discharge adjustment unit 28, adjust the flow of the water from the water storage tank supply.And, auxiliary sets
Standby unit 4 possesses：Gas stop valve 32, blocks the fuel gas supplied from the fuel supply source 30 of town gas etc.；Devulcanizer
36, for removing desulfuration from fuel gas；And fuel flow rate adjustment unit 38, adjust the flow of fuel gas.Auxiliary equipment list
Unit 4 is also equipped with：Electromagnetic valve 42, blocks the oxidant i.e. air from the supply of air supply source 40；Reformation both air flow modulation list
Unit 44 and generating both air flow modulation unit 45, adjust the flow of air；1st heater 46, heats and is supplied to reformer 20
Reformation air；And the 2nd heater 48, heat the generating air to power compartment supply.Above-mentioned 1st heater 46 and the 2nd
Intensification when heater 48 is to efficiently be started and arrange, but can also omit.
Next, being connected with warm water manufacture device 50 on fuel cell module 2, it is supplied to discharge gas.The warm water
Manufacture device 50 is supplied to the tap water from watering 24, and the tap water becomes warm water due to the heat of discharge gas, and
It is supplied to the thermal storage water tank of outside hot water supply device (not shown).And, control chamber 52 is installed on fuel cell module 2,
It is used to control quantity delivered of fuel gas etc..And, electric power leading-out portion is connected with fuel cell module 2（Electrical power conversion
Portion）That is inverter 54, it is used for being externally supplied the electric power that sent by fuel cell module.
Next, according to Fig. 4 and Fig. 6, illustrating the inside of the fuel cell module of solid oxide fuel cell system
Structure.Fig. 4 is the side view cutaway drawing of the fuel cell module for representing solid oxide fuel cell system, and Fig. 6 is along Fig. 4
The sectional view of III-III lines.As shown in Fig. 4 and Fig. 6, in the sealing space 8 of the housing 6 of fuel cell module 2, as above institute
State, be configured with aggregate 12, reformer 20, air heat exchanger 22 successively from below.
Reformer 20 is provided with the pure water ingress pipe 60 for importing pure water to its upstream side and will weigh for importing
Whole fuel gas and reformation air are reformed gas introduction tube 62, and, the inside of reformer 20 from upstream side according to
It is secondary to be formed with evaporation part 20a and reforming section 20b, it is filled with reforming catalyst in reforming section 20b.Import the mixing of the reformer 20
The fuel gas and air for having vapor is reformed by the reforming catalyst being filled in reformer 20.
Fuel gas supply pipe 64 is connected with the downstream side of the reformer 20, the fuel gas supply pipe 64 is downwards
Extend, so it is horizontal-extending in the diverter 66 being formed at below aggregate 12.Supply in fuel gas
Multiple fuel supply hole 64b are formed with to the lower aspect of the horizontal part 64a of pipe 64, from the fuel supply hole 64b to diverter 66
Fuel gas after interior supply reformation.
It is provided with for support above-mentioned fuel cell pile 14 lower that possesses through hole in the top of the diverter 66
Fagging 68, the fuel gas in diverter 66 is supplied in fuel-cell single-cell unit 16.
Next, being provided with air heat exchanger 22 in the top of reformer 20.Air heat exchanger 22 is in upstream side
Possess collect air room 70, possess 2 air chambers 72 in downstream, above-mentioned collect air room 70 and air chamber 72 are logical
Cross 6 air flow circuit pipes 74 and connect.Here, as shown in fig. 6,3 air flow circuit pipes 74 become one group（74a、74b、74c、
74d、74e、74f）, the air in collect air room 70 flows into respective air chamber 72 from each group air flow circuit pipe 74.
The air of flowing is risen using burning in combustor 18 in 6 air flow circuit pipes 74 of air heat exchanger 22
Discharge gas preheated.Air leading-in conduit 76 is connected with each air chamber 72, the air leading-in conduit 76 is downward
Fang Yanshen, its lower end side is connected with the underlying space of power compartment 10, and to power compartment 10 air after preheating is imported.
Next, in the discharge gas room 78 formed below of diverter 66.And, as shown in fig. 6, growing along housing 6
The face i.e. above 6a and the below inner side of 6b in degree direction, is formed with the discharge gas path 80 for extending in the vertical direction, the row
The upper end side for putting gas passage 80 is connected with the space for being configured with air heat exchanger 22, and lower end side connects with discharge gas room 78
It is logical.And, substantial middle is connected with discharge gas discharge pipe 82 below discharge gas room 78, the discharge gas discharge pipe 82
Downstream be connected to above-mentioned warm water manufacture device 50 shown in Fig. 3.As shown in figure 4, for starting fuel gas and air
The igniter 83 of burning is arranged at combustor 18.
Below, fuel cell pile 14 is illustrated according to Fig. 5.Fig. 5 is to represent SOFC system
The axonometric chart of the fuel cell pile of system.As shown in figure 5, fuel cell pile 14 possesses 16 fuel-cell single-cell units
16, the lower end side and upper end side of these fuel-cell single-cell units 16 is respectively by ceramic lower supporting plate 68 and upper backup pad
100 support.It is respectively formed with the through hole that medial electrode terminal 86 can run through on gripper shoe 68 and upper backup pad 100 in these lower
68a and 100a.
And, collector 102 and outside terminal 104 are installed on fuel-cell single-cell unit 16.The collector 102
By be installed on fuel electrodes that the fuel electrodes i.e. medial electrode terminal 86 of medial electrode layer 90 electrically connects connecting portion 102a and with
Air pole is that the air pole connecting portion 102b that the outer peripheral face of lateral electrode layer 92 is integrally electrically connected is integrally formed.Air pole is used
Connecting portion 102b is by the vertically extending vertical portion 102c in the surface of outer Side-electrode layer 92 and from the vertical portion 102c edges
Many horizontal part 102d that the surface of lateral electrode layer 92 extends in the horizontal direction are formed.And, fuel electrodes connecting portion
102a from air pole with the vertical portion 102c of connecting portion 102b towards fuel-cell single-cell unit 16 positioned at above-below direction
Medial electrode terminal 86, obliquely upward or obliquely downward straight-line extension.
And, positioned at the one end of fuel cell pile 14（Left end inboard and with front side in Fig. 5）2 fuel cell lists
Outside terminal 104 is connected on the upside of battery unit 16 and the medial electrode terminal 86 of lower side.These outer ends
The outside terminal 104 of son 104 and the fuel-cell single-cell unit 16 positioned at adjacent one end of fuel cell pile 14（Do not scheme
Show）Connection, as described above, 160 fuel-cell single-cell units 16 are all connected in series.
Below, the starting pattern of the fuel cell system to illustrating is illustrated.First, control reformation to be adjusted with air mass flow
Section unit 44, electromagnetic valve 42 and mixing unit 47, to increase reformation air, to reformer 20 air are supplied.In addition, control generates electricity
With both air flow modulation unit 45, electromagnetic valve 42, generating air is supplied from air leading-in conduit 76 to power compartment 10.Then, control
Fuel flow rate adjustment unit 38 processed and mixing unit 47, to increase the supply of fuel gas, to the supply of reformer 20 gas are reformed,
Be admitted to reformer 20 is reformed gas and reformation air via reformer 20, fuel gas supply pipe 64, gas distribution
Device 66, is admitted in each fuel-cell single-cell unit 16 from each through hole 69.It is admitted to each fuel-cell single-cell unit
In 16 gas and reformation air are reformed from the fuel gas channel for being formed in each lower end of fuel-cell single-cell unit 16
98 flow out respectively through fuel gas channel 88 from the fuel gas channel 98 for being formed in upper end.Thereafter, by igniter
83 make to perform burning operation from being reformed gas ignition of the upper end of fuel gas channel 98 outflow.Thus, in combustor 18
Make to be reformed gas combustion, part oxyreforming reaction occurs.
Thereafter, more than about 600 DEG C are reached with the temperature of reformer 20, and the temperature of aggregate 12 surpasses
About 250 DEG C are crossed for condition, autothermal reforming reaction is proceeded to.Now, by discharge adjustment unit 28, fuel flow rate adjustment unit 38
And reform with both air flow modulation unit 44, it has been pre-mixed to the supply of reformer 20 and has been reformed gas, reformation air and water
The gas of steam.Next, reaching more than 650 DEG C, and the temperature of aggregate 12 with the temperature of reformer 20
It is condition that degree exceedes about 600 DEG C, proceeds to steam reforming reaction.
As described above, start to change reforming process according to the progress of burning operation from lighting, thus in power compartment 10
Temperature is gradually increasing.The temperature of power compartment 10 reaches the rated temperature than making the steady operation of fuel cell module 2（About 700 DEG C）It is low
Regulation power generation temperature after, closure includes the circuit of fuel cell module 2.Thus, fuel cell module 2 starts to generate electricity, can
Electric current is flow through in circuit and to externally fed.
Below, the operation of the solid oxide fuel cell system of present embodiment is stopped illustrating.Fuel electricity
The operation of cell system stop be stop from fuel cell module derive electric power after also sustainable supply fuel, and by a large amount of conveyings
Tempering air is cooling down fuel cell pile.Next, making stack temperature deteriorate to less than the fuel of fuel-cell single-cell
Fuel supply during the oxidizing temperature of pole stops, and afterwards, only continues to supply tempering air before temperature fully declines, can be with
Fuel cell is set to stop completely.
In addition, being stopped substantially while blocking electric power derivation, fuel gas, air and fuel weight by shutdown when urgent
The supply of whole use water, then stop can fuel cell system.In addition, electric power is derived after stopping can also phase down fuel
And stopped, or without flow through N2The purification gas of gas etc. are just stopped.
What shutdown stopped substantially refers to that electric current, air, gas, water are very short within 10 seconds while carrying out blocking
It is wholly off in time.More specifically, it is to stop operation as follows, after interruptive current after more than ten seconds, interrupt air and
The supply of fuel gas, and then interrupt water supply after it is more than ten seconds.
Embodiment
The present invention is explained in more detail by below example, but the invention is not limited in these embodiments.
Embodiment 1
The making of air pole slurry
By to La0.6Sr0.4Co0.2Fe0.8O3The material powder of composition, solvent, binding agent, as two fourths of sulphur compound
Sodium dioctyl sulfo carries out co-grinding to make air pole slurry.Here, adjusting and adding the amount of sulphur compound, make just
The sulfur content in air pole after just burning till is 50ppm.
The making of SOFC monocell
Compare 65 with weight：35 mixing NiO powder and 10YSZ（10mol%Y2O3-90mol%ZrO2）Powder, by being squeezed into
Shape machine applies shearing and carries out primary particle and be configured to cylindrical shape, is calcined with 900 DEG C and has been made fuel electrodes support
Body.The fuel electrode catalyst layer of the reaction for promoting fuel electrodes is formed with the fuel electrodes supporter.On fuel electrodes supporter,
By slurry coating method to comparing 50 with weight：50 are mixed with NiO and GDC10（10mol%Gd2O3-90mol%CeO2）Material enter
Row masking is so as to forming fuel electrode catalyst layer.Further, by slurry coating method in fuel electrodes catalytic reaction oxidant layer layer successively
Folded LDC40（40mol%La2O3-60mol%CeO2）、La0.8Sr0.2Ga0.8Mg0.2O3The LSGM of composition, forms solid electrolyte layer,
Formed body is obtained.Resulting formed body is burnt till with 1300 DEG C.Thereafter, air pole is starched by slurry coating method
Material is filmed, and by being burnt till with 1050 DEG C SOFC has been made.
Sulfur content in air pole is to cut the air pole after the burning till of fuel-cell single-cell, by analysis of carbon and sulfur device
To determine the sulfur content remained in air pole.In addition, from the fuel cell list being coated with air pole after the completion of current collection layer
When battery determines sulfur content, air pole can be cut, and determine sulfur content.
Made SOFC monocell is as follows.Fuel electrodes supporter is external diameter 10mm, thickness
Degree 1mm.The thickness of fuel electrodes catalytic reaction oxidant layer is 20 μm.The thickness of LDC layers is 5 μm.The thickness of LSGM layers is 30 μm.Air
The thickness of pole is 25 μm, and the area of air pole is 35cm2。
Next, coating liquid is applied in air pole so as to form air pole current collection layer.The composition of coating liquid is combined silver
Powder, palladium powder, LSCF powder, solvent and binding agent.The coating liquid is coated in into solid oxide fuel by aerosol apparatus
After on cell single cells, it is dried by drying machine, after cooling down at room temperature, carries out 1 hour burning till with 700 DEG C, in air
The outside of pole forms air pole current collection layer.Air pole current collection layer possesses silver, palladium and LSCF.
The making of SOFC module
The electric conductivity encapsulant for having collector and gas seal member concurrently is installed at the both ends of fuel electrodes supporter, and then front
The both ends for stating fuel electrodes arrange medial electrode terminal, to cover electric conductivity encapsulant, so as to make fuel cell list electricity
Pool unit.The internal diameter phase diameter group of medial electrode terminal and the fuel electrodes supporter for becoming fuel gas channel reduces, with from
The reducing diameter part that each end of aforementioned monocell extends to monocell lateral direction.Make 16 aforementioned fuel cells single cell units
For one group, it is connected in series 16 by the adapter of connection fuel electrodes and air pole and realizes pile.Carry 10 groups of aforementioned electricity
Heap and make 160 to be connected in series, and then coated with housing after reformer, air line and fuel distribution tube are installed, made solid
Oxide body type fuel cell module.The fuel cell module is assembled to into solid oxide fuel cell system.
The power generation test of SOFC monocell
Using resulting SOFC monocell（Electrode effective area：35.0cm2）, generated electricity
Test.The current collection of fuel electrodes circumferentially winds Ag lines and carries out on medial electrode terminal.The current collection of air pole be also
Ag lines are circumferentially wound on air pole current collection layer and carry out.Power generation conditions are as follows.That is, fuel gas is fuel（H2+3%
H20）And N2Mixed gas, fuel availability is 75%.In addition, oxidant gas are air.Temperature of the measurement is 700 DEG C, is determined
Electric current density 0.2A/cm2Under generating current potential.The initial performance of monocell is expressed as into initial potential in table 1.
Shutdown test
After made fuel cell system is run as follows, shutdown stopping is carried out.Then, visually confirm in module
The outward appearance of SOFC monocell.
Fuel cell system generates electricity
Fuel gas is set to be Cities of Japan coal gas 13A, fuel availability is 75%.In addition, oxidant is air, air profit
It is 40% with rate.S/C=2.25.Generating steady temperature is 700 DEG C, with electric current density 0.2A/cm2Run.
Fuel cell system stops
Run 2 hours afterwards with steady temperature, by shutdown stop substantially blocking simultaneously the electric current of fuel cell system,
Fuel gas, the supply of empty gas and water and stop fuel cell system.Thereafter, the module in extraction system, visually confirms internal
SOFC monocell outward appearance.Outward appearance is evaluated by following benchmark.
Evaluate excellent：The shutdown of more than 100 times generates electricity after stopping and also do not have obstacle and air pole stripping, monocell do not occur
It is damaged.
Evaluate good：Shutdown less than 100 times generates electricity after stopping and also do not have obstacle and do not find air pole stripping, monocell
Breakage, though the shutdown more than 100 times does not result in air pole stripping in stopping, but confirms floating for air pole（Rise
Wrinkle）.
Evaluate fine：Shutdown less than 5 times generates electricity after stopping and also do not have obstacle and do not find that air pole is peeled off, monocell breaks
Damage, though the shutdown more than 5 times does not result in air pole stripping in stopping, but confirm floating for air pole（Corrugation）.
Evaluate poor：Confirm that air pole is peeled off in the shutdown less than 5 times stops.
Result above is as shown in the table 1 recorded below.
Embodiment 2
Except adjusting and adding the amount of sulphur compound, the sulfur content in the air pole after burning till is set to be beyond 100ppm, with reality
Apply example 1 and similarly make SOFC monocell and fuel cell system.Then, carry out and embodiment 1
Same test.As a result as shown in the table 1 recorded below.
Embodiment 3
Except adjusting and adding the amount of sulphur compound, the sulfur content in the air pole after burning till is set to be beyond 200ppm, with reality
Apply example 1 and similarly make SOFC monocell and fuel cell system.Then, carry out and embodiment 1
Same test.As a result as shown in the table 1 recorded below.
Embodiment 4
Except adjusting and adding the amount of sulphur compound, the sulfur content in the air pole after burning till is set to be beyond 500ppm, with reality
Apply example 1 and similarly make SOFC monocell and fuel cell system.Then, carry out and embodiment 1
Same test.As a result as shown in the table 1 recorded below.
Embodiment 5
Except adjusting and adding the amount of sulphur compound, the sulfur content in the air pole after burning till is set to be beyond 1,000ppm, with
Embodiment 1 has similarly made SOFC monocell and fuel cell system.Then, carry out and embodiment
1 same test.As a result as shown in the table 1 recorded below.
Embodiment 6
Except adjusting and adding the amount of sulphur compound, the sulfur content in the air pole after burning till is set to be beyond 3,000ppm, with
Embodiment 1 has similarly made SOFC monocell and fuel cell system.Then, carry out and embodiment
1 same test.As a result as shown in the table 1 recorded below.
Comparative example 1
As the material of air pole, by La0.6Sr0.4Co0.2Fe0.8O3The powder of composition, solvent and binding agent are carried out
Co-grinding and be prepared for air pole slurry.Make using resulting slurry and by method similarly to Example 1
SOFC monocell and fuel cell system.Sulfur content in the air pole of resulting monocell is
10ppm.Then, test similarly to Example 1 is carried out.As a result as shown in the table 1 recorded below.
Comparative example 2
Except adjusting and adding the amount of sulphur compound, the sulfur content in the air pole after burning till is set to be beyond 5,000ppm, with
Embodiment 1 has similarly made SOFC monocell and fuel cell system.Then, carry out and embodiment
1 same test.As a result as shown in the table 1 recorded below.
Table 1
Embodiment 8
To become La0.6Sr0.4Co0.2Fe0.8O3Ratio of components mode, weighing becomes the lanthana of raw material（La2O3）, carbon
Sour strontium（SrCO3）, cobalt carbonate（CoCO3）And ferrum oxide（Fe2O3）Powder and the two butanoic acid dioctyl ester sulphurs as sulphur compound
Sour sodium, is mixed in the solution.Thereafter, powder obtained from removing solvent is burnt till with 1200 DEG C, and is crushed,
Thus the air pole material powder containing sulfur has been made.Here, the organosulfur compound contained in air pole material powder is adjusted,
The sulfur content in air pole after burning till fuel-cell single-cell is 50ppm.By to resulting material powder, solvent and
Binding agent carries out co-grinding to prepare air pole slurry.Make using the air pole slurry and similarly to Example 1
SOFC monocell and fuel cell system.Then, test similarly to Example 1 is carried out.As a result
As shown in the table 2 recorded below.
Embodiment 9
Except adjusting and adding the amount of sulphur compound, the sulfur content in the air pole after burning till is set to be beyond 100ppm, with reality
Apply example 8 and similarly make SOFC monocell and fuel cell system.Then, carry out and embodiment 1
Same test.As a result as shown in the table 2 recorded below.
Embodiment 10
Except adjusting and adding the amount of sulphur compound, the sulfur content in the air pole after burning till is set to be beyond 200ppm, with reality
Apply example 8 and similarly make SOFC monocell and fuel cell system.Then, carry out and embodiment 1
Same test.As a result as shown in the table 2 recorded below.
Embodiment 11
Except adjusting and adding the amount of sulphur compound, the sulfur content in the air pole after burning till is set to be beyond 500ppm, with reality
Apply example 8 and similarly make SOFC monocell and fuel cell system.Then, carry out and embodiment 1
Same test.As a result as shown in the table 2 recorded below.
Embodiment 12
Except adjusting and adding the amount of sulphur compound, the sulfur content in the air pole after burning till is set to be beyond 1,000ppm, with
Embodiment 8 has similarly made SOFC monocell and fuel cell system.Then, carry out and embodiment
1 same test.As a result as shown in the table 2 recorded below.
Embodiment 13
Except adjusting and adding the amount of sulphur compound, the sulfur content in the air pole after burning till is set to be beyond 3,000ppm, with
Embodiment 8 has similarly made SOFC monocell and fuel cell system.Then, carry out and embodiment
1 same test.As a result as shown in the table 2 recorded below.
Comparative example 3
Except adjusting and adding the amount of sulphur compound, the sulfur content in the air pole after burning till is set to be beyond 5,000ppm, with
Embodiment 8 has similarly made SOFC monocell and fuel cell system.Then, carry out and embodiment
1 same test.As a result as shown in the table 2 recorded below.
Table 2
Claims (8)
1. a kind of SOFC monocell, is structure at least with solid electrolyte, fuel electrodes and air pole
Into SOFC monocell, it is characterised in that
The air pole is the formed body containing perofskite type oxide and element sulphur to be burnt till and is constituted,
Sulfur content in the air pole generated electricity before starting is more than 50ppm and below 3,000ppm.
2. SOFC monocell according to claim 1, it is characterised in that the element sulphur from
The sulphur compound separately coordinated with perofskite type oxide.
3. SOFC monocell according to claim 1, it is characterised in that the element sulphur from
The sulphur compound contained in the preparing raw material of perofskite type oxide.
4. SOFC monocell as claimed in any of claims 1 to 3, it is characterised in that
The perofskite type oxide is lanthanum-strontium Conjugate ferrite i.e. LSCF.
5. SOFC monocell according to claim 1, it is characterised in that the sulfur content
For more than 100ppm and below 3,000ppm.
6. a kind of fuel cell system, it is characterised in that possess the soild oxide described in any one in claim 1 to 5
Type fuel-cell single-cell and constitute.
7. a kind of manufacture method of SOFC monocell, is in claim 1 to 5 described in any one
The manufacture method of SOFC monocell, it is characterised in that
Prepare the material powder that sulphur compound is added with perofskite type oxide,
The material powder is disperseed in a solvent so as to prepare slurry,
The slurry is coated on solid electrolyte or its precursor, and after being dried, is burnt till to prepare air pole.
8. a kind of manufacture method of SOFC monocell, is in claim 1 to 5 described in any one
The manufacture method of SOFC monocell, it is characterised in that
Mixture to being added with sulphur compound in the preparing raw material of perofskite type oxide burns till, so as to be contained
The perofskite type oxide of element sulphur,
Crush the perofskite type oxide and obtain material powder,
The material powder is disperseed in a solvent so as to prepare slurry,
The slurry is coated on solid electrolyte or its precursor, and after being dried, is burnt till to prepare air pole.
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| US9678501B2 (en) * | 2013-01-08 | 2017-06-13 | Bloom Energy Corporation | Serialization of fuel cell components |
| JP2016054146A (en) * | 2014-09-02 | 2016-04-14 | Toto株式会社 | Solid oxide fuel battery system |
| WO2016144067A1 (en) * | 2015-03-06 | 2016-09-15 | 주식회사 엘지화학 | Method for manufacturing electrode, electrode manufactured by same, electrode structure including electrode, fuel cell or metal-air secondary battery, battery module including cell or battery, and composition for manufacturing electrode |
| WO2017006943A1 (en) * | 2015-07-07 | 2017-01-12 | 日本碍子株式会社 | Fuel cell |
| KR102169225B1 (en) * | 2016-08-08 | 2020-10-23 | 모리무라 에스오에프씨 테크놀로지 가부시키가이샤 | Electrochemical reaction single cell and electrochemical reaction cell stack |
| GB2557344B (en) * | 2016-12-08 | 2021-05-19 | Ceres Ip Co Ltd | Anode |
| JP2018125284A (en) * | 2017-02-01 | 2018-08-09 | Toto株式会社 | Solid oxide fuel battery cell |
| JP6999518B2 (en) * | 2017-08-10 | 2022-01-18 | 森村Ｓｏｆｃテクノロジー株式会社 | Solid oxide fuel cell |
| JP7430477B2 (en) * | 2017-08-10 | 2024-02-13 | 森村Ｓｏｆｃテクノロジー株式会社 | solid oxide fuel cell |
| JP7015125B2 (en) * | 2017-08-10 | 2022-02-02 | 森村Ｓｏｆｃテクノロジー株式会社 | Pneumatic material and solid oxide fuel cell |
| JP6690795B1 (en) * | 2018-09-27 | 2020-04-28 | 堺化学工業株式会社 | Powder for solid oxide fuel cell air electrode and method for producing the same |
| CN113661144B (en) * | 2019-03-25 | 2023-11-07 | 堺化学工业株式会社 | Metal composite oxide, method for producing same, and electrode for solid oxide fuel cell |
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| EP2741360A2 (en) | 2014-06-11 |
| US20140162149A1 (en) | 2014-06-12 |
| EP2741360A3 (en) | 2014-10-15 |
| JP2017195190A (en) | 2017-10-26 |
| US9515322B2 (en) | 2016-12-06 |
| JP2014135271A (en) | 2014-07-24 |
| EP2741360B1 (en) | 2017-03-08 |
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